A solid crystallizes when it freezes in a solution, which involves molecules of one type falling into a regular orientation with one another to the exclusion of all different molecules. The thermal agitation of the molecules works against this tendency, and freezing occurs when the ordering forces of hydrogen bonding or other intermolecular forces overcome the disordering forces of thermal agitation. Similar intermolecular attractions can lead to the formation of two liquid phases if the intermolecular forces are large enough to exclude other molecules but still too small to completely overcome thermal agitation. Such miscibility gaps form over a broad temperature range when the molecules in a solution exhibit large differences in, for example, dipole moments or even shape and size. More similar liquid-phase molecules, normally partially or completely miscible, can also split into two phases as their temperature approaches the point at which a component freezes, which generally is lower than the pure component freezing temperature. While no liquid mixtures are ever completely immiscible, when a liquid mixture is substantially at the temperature at which a component freezes, the components in the mixture become essentially immiscible. In other words, their partial miscibility approaches zero as the temperature approaches the component freezing temperature. However, the inventors are unaware of any process currently utilizing these near freezing liquid-liquid interactions to separate otherwise partially or fully miscible liquids.
U.S. Pat. No. 3,653,222 to Blair, et al., teaches a method of freezing solution droplets and the like using immiscible refrigerants of differing densities. The invention includes the freezing of liquid dispersions, including dispersions on the ionic scale of salt solutions on through fluid colloidal systems. Appropriate materials that are soluble in a solvent for which two mutually immiscible, denser liquid refrigerants exist, and that are also individually immiscible with the solvent, may be processed. The present disclosure differs from this prior art disclosure in that the purpose of this prior art disclosure is to freeze liquid dispersions, not to separate components from each other nor to do liquid-liquid separations. This prior art disclosure is pertinent and may benefit from the methods disclosed herein and is hereby incorporated for reference in its entirety for all that it teaches.